Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

• Aromatic carbonate polymers are Well known, cornmercially available materials having a variety of applications in the plastics art. Such carbonate polymers may be prepared by reacting a dihydric phenol, such as 2,2 bis-(4-hydroxyphenyl) propane (Bisphenol A), with a carbonate precursor such as phosgene, in the presence of an acid acceptor. Generally speaking, aromatic polycarbonate resins oflfer a high resistance to the attack of mineral acids, may be easily molded, and are physiologically harmless as well as stain resistant. In addition, such polymers have a high impact strength, a high heat resistance, and a dimensional stability far surpassing that of any other commercially available thermoplastic material.
• a dihydric phenol such as 2,2 bis-(4-hydroxyphenyl) propane (Bisphenol A)
• phosgene phosgene
• polycarbonate resins have rendered them particularly useful in the production of photographic film base.
• polycarbonates possess excellent color, clarity, and dimensional stability over a Wide range of temperatures and humidity, and are thus Well suited in photographic film applications.
• due to the warping and dimensional changes that occasionally occur during the developing and processing of photographic film there has been considerable demand for a polycarbonate film having a greater stilfness and a higher tensile modulus.
• the rigidity and stiffness of the thermoplastic resin compositions may be increased by the addition of inorganic fillers to such compositions.
• Bostwick and Cary disclose the addition of silicas, carbon black, clays, and calcium and magnesium carbonates to polyethylene for the purpose of imparting increased rigidity and stiffness thereto.
• the filled compositions were more rigid but had lower elongations and tear strengths than the unfilled compositions.
• the addition of such inorganic fillers to polycarbonate resin results in an increase in the rigidity of the polycarbonate with a corresponding decrease in the elongation and tear strength.
• the most serious deficiency of such filled polycarbonate resin compositions is that they may not be solution cast into transparent film form suitable for use in photographic film applications.
• the resultant mixture may be solution cast to provide clear films exhibiting tensile moduli of 300,000 p.s.i. or greater (5" gage) which are suitable for use in the production of photographic film base.
• tensile moduli 300,000 p.s.i. or greater (5" gage) which are suitable for use in the production of photographic film base.
• my invention it has been found that a significant increase in modulus is obtained when the modifier is added to the polycarbonate resin in amounts ranging from about 5% to about 40% by weight (of the polycarbonate resin and modifier).
• films of the resinous mixtures of the invention may be readily prepared by casting a solution of the resinous mixture onto a stationary substrate, as for example, a smooth glass or metal surface, and moving a doctor blade across the substrate surface to smooth out the solution layer. The organic solvent may then be removed to leave the desired polycarbonate film.
• the organic solvent solution of mixtures of the invention may be prepared by first admixing the modifier with the polycarbonate by any of the above-mentioned mixing techniques, and subsequently dissolving the resinous mixture in the organic solvent, or, alternatively, by adding each component of the mixture (i.e., polycarbonate and modifier) individually to the organic solvent.
• any volatile organic solvent inert in the sense that it does not affect the carbonate polymer or a modifier employed, but in which both are soluble, may be used in the film casting process.
• suitable solvents are: methylene chloride, 1,2-dichloroethylene, and chloroform.
• the ortho-ortho alkylidene bridged novolac polymers falling within the scope of Formula I may be prepared by condensing a phenol having its para position blocked by either an alkyl or an aryl radical, with an aldehyde under standard novolac producing conditions.
• Novolac polymers have repeating structural units of the formula OH as i.e., where n is 0 in Formula I above, may be prepared, for example, by employing a p-halogen phenol in the standard novolac producing reaction, and subsequently removing the halogen from the para position by any of the well known reduction techniques.
• the phenol used for preparing the ortho-ortho novolacs utilized in the present invention may be any phenol in which the sole reactive group is the phenolic hydroxyl group and in which the two ortho positions of the aromatic nucleus to which the hydroxyl group is attached are reactive in the condensation with an aldehyde.
• any substituted or unsubstituted aldehyde in which the sole reactive group is the carbonyl group may be employed to provide the ortho-ortho novolacs used in the practice of the invention.
• aldehydes which may be used are, for instance, formaldehyde, acetaldehyde, benzaldehyde, and butyraldehyde.
• Other phenols and aldehydes which may be employed to provide such novolac polymers will readily occur to those skilled in the art.
• linear novolac resins are the novolac polymers prepared by condensing a phenol which is substituted with an alkyl or an aryl group in the ortho position with an aldehyde under standard novolac producing conditions.
• linear novolac resins are the condensation products of a phenol such as ortho cresol and ortho-tertiary-butyl phenol with aldehydes such as formaldehyde or acetaldehyde.
• linear novolac polymers as used herein embraces the ortho-ortho novolac polymers such as, for example, those falling within the scope of Formula I, as well as the novolac resins prepared by reacting aldehydes with ortho substituted phenols, or with para substituted phenols, or with mixtures of ortho substituted and para substituted phenols under standard novolac producing conditions.
• the coumarone-indene resins suitable for use in the preparation of the resinous mixtures of the invention are well known materials and may be prepared by the direct polymerization of coumarone and indene in the presence of catalysts such as sulfuric acid, phosphoric acid or BF for example. Such resins are described in German Patents 392,092 and 394,217 as well as US. Patent 1,541,266. Further description of the coumarone-indene resins suitable for use in the practice of the invention may be found in Synthetic Resins and Allied Plastics, Chapter VII, Oxford University Press, 1943. Although the coumaroneindene resins may vary in composition, molecular weight and molecular weight distribution, the series used most advantageously in the practice of the invention have softening temperatures above about 75 C. and a specific gravity above 1.06.
• the phenol modified coumarone-indene resins useful in the practice of the invention are also well known materials and are described in Industrial and Engineering Chemistry, 30, 1228-1232 (1938), in German Patent 302,543, as well as US. Patents 1,754,052 and 1,857,333. Although these resins may vary in composition, molecular weight and molecular weight distribution, the series which are preferred in the practice of the present invention have softening temperatures above about 50 C. and a specific gravity above 1.1.
• acetylated linear novolac polymers useful in the preparation of the resinous compositions of the invention may be prepared by reacting acetic anhydride with any one of the linear novolac polymers referred to above. For instance, acetic anhydride may be added to a vessel containing a linear novolac polymer and the mixture refluxed until the reaction is complete. The quantity of acetic anhydride used should be sufiicient to react with all of the available hydroxyl groups of the linear novolac polymers.
• the high molecular weight aromatic carbonate polymers used to provide polycarbonate mixtures of the present invention may be prepared by reacting a dihydric phenol with a carbonate precursor such as phosgene, a haloformate or a carbonate ester.
• carbonate polymers may be typified as possessing recurring structural units of the formula where A is a divalent aromatic radical of the dihydric phenol employed in the polymer producing reaction.
• high molecular weight aromatic carbonate polymers I refer to carbonate polymers having intrinsic viscosities (as measured in p-dioxane in deciliters per gram at 30 C.) greater than about 0.40 and preferably, above about 0.50.
• the dihydric phenols which may be employed to provide such aromatic carbonate polymers are mononuclear or polynuclear aromatic compounds, containing as functional groups, 2 hydroxyl radicals, each of whichis attached directly to a carbon atom of an aromatic nucleus.
• Typical dihydric phenols are 2,2 bis-(4-hydroxyphenyl)- propane; 2,2 bis-(4-hydroxyphenyl)-pentane; 2,2 bis-(4- hydroxy 3 methyl phenyl) propane; 2,2 bis (4 hydroxy 3,5 dichloro phenyl) propane; 2,2 bis (4 hydroxy 3,5 dibromo phenyl) propane; 1,1 bis-(4-hydroxyphenyl)-ethane; 4,4 dihydroxy 3,3 dichloro diphenyl ether.
• a variety of additional dihydric phenols which may be employed to provide such carbonate polymers are disclosed in US. Patent 2,999,835, Goldberg, assigned to the assignee of the present invention.
• the materials are reacted at temperatures of from 100 C. or higher for times Varying from 1 to 15 hours. Under such conditions ester interchange occurs between the carbonate ester and the dihydric phenol used.
• the ester interchange is advantageously consummated at reduced pressures of the order of from about to about 100 mm. of mercury, preferably in an inert atmosphere, such as nitrogen or argon, for example.
• ester exchange catalysts such as, for example, metallic lithium, potassium, calcium and magnesium. Additional catalysts and variations in the exchange methods are discussed in Groggins, Unit Processes in Organic Synthesis (4th edition, McGraw-Hill Book Company, 1952) pages 616 to 620.
• the amount of such catalyst, if used, is usually small, ranging from about 0.001 to about 0.1%, based on the moles of the dihydric phenol employed.
• the carbonate ester useful in this connection may be aliphatic or aromatic in nature, although aromatic esters, such as diphenyl carbonate, are preferred. Additional examples of carbonate esters Which may be used are dimethyl carbonate, diethyl carbonate, phenylmethyl carbonate, phenyltolyl carbonate and di (tolyl) carbonate.
• a preferred method for preparing the carbonate polymers suitable for use in providing the high modulus polycarbonate mixtures of the present invention involves the use of a carbonyl halide, such as phosgene, as the carbonate precursor.
• This method involves passing phosgene .gas into a reaction mixture containing the dihydric phenol and an acid acceptor such as a tertiary amine (e.g., pyridine, dimethylaniline, quinoline etc.)
• the acid acceptor may be used undiluted or diluted with inert organic solvents as, for example, methylene chloride, chlorobenzene, or 1,2 dichloroethane.
• Tertiary amines are advantageous since they are good solvents as well as acid acceptors during the reaction.
• the temperature at which the carbonyl halide reaction proceeds may vary from below 0 C. to above C.
• the reaction proceeds satisfactorily at temperatures from room temperature (25 C.) to 50 C. Since the reaction is exothermic, the rate of phosgene addition may be used to control the reaction temperature.
• the amount of phosgene required will generally depend upon the amount of dihydric phenol present. Generally speaking, one mole of phosgene will react with one mole of the dihydric phenol used to provide the polymer and two moles of HCl. Two moles of HCl are in turn attached by the acid acceptor present. The foregoing are herein referred to as stoichiometric or theoretical amounts.
• Another method for preparing the carbonate polymers which maybe used to provide the high-modulus polycarbonate resin mixtures of the invention comprises adding phosgene to an alkaline aqueous suspension of the dihydric phenol used. This is preferably done in the presence of inert solvents such as methylene chloride, 1,2 dichloroethane and the like. Quaternary ammonium compounds may be employed to catalyze the reaction.
• a fourth method for preparing such carbonate polymers involves the phosgenation of an agitated suspension of the anhydrous alkali salts of the dihydric.- phenol used in a non-aqueous medium such as benzene, chlorobenzene, and toluene. This reaction is illustrated by the addition of phosgene to a slurry of the sodium salt of 2,2 bis-(4-hydroxyphenyl)-propane in an inert polymer solvent such as chlorobenzene.
• the organic solvent should preferably be a polymer solvent but need not necessarily be a good solvent for the reactants.
• haloformates of dihydric phenols such as the bishaloformate of 2,2 bis-(4-hydroxyphenyl)-propane, for example, may be substituted for phosgene as the carbonate precursor in any of the methods described above.
• the carbonate polymer emerges from the reaction in either a true or pseudo solution whether aqueous base or pyridine is used as an acid acceptor.
• the polymer may be precipitated from the solution by adding a polymer nonsolvent, such as heptane or isopropanol. Alternatively, the polymer solution may be heated to evaporate the solvent.
• the tensile modulus was calculated by drawing a tangent to the initial linear portion of the load extension curve, selecting any point on this tangent and dividing the tensile strength (nominal) by the corresponding strain. The result is expressed in pounds per square inch and is reported to three significant figures. As will be appreciated by those skilled in the art, the values of the tensile moduli as used herein are comparative in nature and will depend upon the size of the sample tested, the rate of testing and the temperature at which the tests are conducted.
• Example 1 100 parts of EPA polycarbonate powder (1 1:0 in dioxane at 30 C.) was disolved in 400 parts of methylene chloride and the solution filtered and degassed under vacuum to yield a solution having a viscosity of approxi mately 20,000-25,000 centipoises at 25 C. This solution was doctor blade coated from a hopper containing the dope solution onto the clean plate glass surface to produce a dried film of approximately 7-9 mils thickness after air drying 6-72 hours at 25-35 C., 1-2 hours at 80 C., and finally 3 hours at 125 C. in a circulating air oven. Using a 'ITC Instron Testing Machine, the tensile modulus was measured for 1" wide samples using a 5" gage length and found to be 280,000 p.s.i.
• Example 2 100 parts of a polycarbonate copolymer resin (1 1.0 in dioxane at 30 C.) prepared by phosgenating a mixture of EPA (97 parts) and isophthalic acid (3 parts) in pyridine-methylene chloride solution was cast into a film with the procedure described in Example 1. The tensile modulus of this copolymer film was found to be substantially identical to that determined for the EPA polycarbonate used in Example 1.
• Example 3 Several coumarone-indene resins varying in melting point were mixed with the polycarbonate copolymer resin described in Example 2.
• the three coumarone-indene resins used had a melting range of 108-117 C., 110-120 C., 120-130 C., designated A, B and C respectively. Thirty-five parts of each resin was mixed with 65 parts of the polycarbonate copolymer resin and dissolved in 175 ml. methylene chloride. Each of the three solutions were filtered and degassed and cast on the clean plate glass as described above. After drying by the standard procedure, the films had the following tensile modulus values, using a 5 gage length:
• Example 4 Using a phenol modified coumarone-indene resin having a softening point of 76 C. and a specific gravity of 1.144, several mixtures with the polycarbonate resin described in Example 1 were made up as follows:
• Example 5 A similar experiment was performed using a novolac resin prepared by standard techniques using a 0.8 to 1 mole ratio of formaldehyde to pcresol.
• the novolac resin was mixed with the polycarbonate resin described in Example 1, as follows:
• Example 6 35 parts novolac resin prepared from o-cresol and formaldehyde (1 to 0.8 mole ratio) was mixed with 65 parts of the polycarbonate copolymer described in Example 2 and the mixture dissolved in 175 ml. methylene chloride. After casting and drying, the tensile modulus on a 5" gage length was found to be 442,000 .s.i., almost 60% greater than the polycarbonate copolymer containing no additive.
• Example 7 Novola-c resins were prepared by reacting mixtures of p-terL-butylphen-ol and p-cresol with formaldehyde. Two different novolacs J20 parts pt-butylphenol, 80 parts p-oresol. K-10 parts p-t-butylphenol, parts p-cresol.
• each novolac was mixed with the polycarbonate copolymer described in Example 2 (35 parts novolac, 65 parts polycarbonate copolymer). After dissolving each mixture in ml. methylene chloride, casting and drying, the modulus values for each film, using a 5 gage length, were determined to be:
• Example 8 25 parts of a soluble, fusible condensation product of a p-cresol formaldehyde novolac and phosgene, described in my copending application Serial No. 241,131, was mixed with 75 parts of the polycarbonate resin described in Example 1. After dissolving in 300 parts methylene chloride, casting and drying, the resulting film was found to have a tensile modulus of 313,000 .s.i. for a 5" gage length.
• Example 9 100 parts of the o-cresol formaldehyde novolac used in Example 6 was mixed with 160 parts acetic anhydride, 5 drops concentrated sulfuric acid, and heated for 1 /2 hours. The reaction product was precipitated with water, washed to remove excess acetic acid and dried. The dried product showed no phenolic hydroxyl on infrared analysis, indicating essentially complete acetylation. 35 parts of this acetylated novolac was mixed with 65 parts of the polycarbonate copolymer described in Example 2 and the mixture dissolved in 175 ml. methylene chloride. After casting and drying by standard procedure, the film was found to have a tensile modulus on a 5" gage length of 418,000 p.s.i.
• Example 1 Several polycarbonate homopolymers and copolymers, other than those described in Examples 1 and 2, were mixed with a coumarone-indene resin (softening range IDS-117 C.) and the tensile modulus measured on each film. In each case, 2.6 parts of the polymer or copolymer were mixed with 1.4 parts of the coumarone-indene resin and the mixture dissolved in 40 parts methylene chloride, cast in 3" x 5" metal pans, and dried in the usual manner. Four parts of each polymer or copolymer without the additive was dissolved in 40 parts methylene chloride and cast in 3" x 5 metal pans and dried in the usual manner.
• a coumarone-indene resin softening range IDS-117 C.
• the mole ratio shown in column 2 designates the ratio of the reactants (as set forth in column 1) which was phosgenated to provide the desired copolymer.
• the tensile modulus for each film was measured for a 2" gauge length, with result as follows:
• Example 11 709 parts of EPA polycarbonate resin (1 0.58 in dioxane at 30 C.) were mixed with 382 parts coumarone-indene resin (softening point 155 C.) and the mixture extruded in a No. /2 John Royle Extruder at 450-470 F. The extrudate was pelletized and the pellets injected molded into /2" x x 2 /2" bars at 450 500 F. The flexural modulus of these bars was determined to be 420,000 p.s.i. compared to a flexural modulus of 340,000 p.s.i. for the EPA polycarbonate containing no additive.
• the resin mixtures of the invention may be used in the production of any molded part where high structural strength and transparency are required, as for example, fan blades and pump impellers where greater fiexural modulus will reduce flexing and vibration, as Well as housings where greater rigidity imparts greater strength and dimensional stability.
• a resin composition comprising (1) a high molecular weigh-t aromatic polycarbonate resin and (2) from about 5 to about 40% by Weight of a modifier based on the weight of the polycarbonate and said modifier selected from the class consisting of (a) a linear novolac polymer which is soluble in methylene chloride and which is an ortho-ortho alkylidene bridged novolac polymer based on the weight of the polycarbonate and said novolac polymer;
• a resin composition comprising (1) a high molecular weight aromatic polycarbonate resin and p (2) from about 5% to about 40% by weigh-t of a linear novolac polymer which is soluble in methylene chloride and which is an ortho-ortho alkylidene bridged novolac polymer based on the Weight of the polycarbonate and said novolac polymer.
• a resin composition comprising (1) a high molecular weight aromatic polycarbonate resin and (2) from about 5% to about 40% by weight of an .acetylated linear novolac polymer wherein all of the available hydroxyl groups are acetylated based on the weight of the polycarbonate and said novolac polymer.
• a resin composition comprising (1) a high molecular weight aromatic polycarbonate resin and (2) from about 5% to about 40% by weight of a phosgenated ortho-ortho novolac polymer based on the weight of the polycarbonate and said novolac polymer.
• a resin composition comprising (1) a high molecular weight aromatic polycarbonate resin and (2) from about 5% to about 40% by Weight of a coumarone-indene polymer based on the weight of the polycarbonate and said coumarone-indene polymer.
• a resin composition comprising (1) a high molecular weight aromatic polycarbonate resin and (2) from about 5% to about 40% by weight of a phenol modified conmarone-indene polymer based on the Weight of the polycarbonate and said coumarone-indenepolymer.
• a resin composition comprising (1) a high molecular weight aromatic polycarbonate resin and (2) from about 5 to about 40% by weight of a linear novolac polymer which is the condensation product of p-cresol and formaldehyde based on the weight of the poly-carbonate and said novolac polymer.
• a resin composition comprising (1) a high molecular weight aromatic polycarbonate resin and (2) from about 5 to about 40% by Weight of a linear novolac polymer which is the condensation product of o-cresol and formaldehyde based on the weight of the polycarbonate and said novolac polymer.
• a resin composition comprising 1) poly (p,p' diphenyl propane) carbonate and (2) from about 5 to about 40% by weight of a modi- 1 l bomb based on the Weight of the polycarbonate in said modifier selected from the class consisting of:
• a method for improving the tensile and flexural moduli of a high molecular weight polycarbonate resin which comprises mixing the resin wtih a modifier comprising at least one member of the class consisting of:

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  • NL NL301734D patent/NL301734A/xx unknown
  • GB GB1052496D patent/GB1052496A/en active Active
• 1962
  • 1962-12-20 US US245960A patent/US3294862A/en not_active Expired - Lifetime
• 1963
  • 1963-12-12 NL NL63301734A patent/NL141225B/xx unknown
  • 1963-12-17 DE DE19631544942 patent/DE1544942B2/de not_active Withdrawn

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